CN107999030A - A kind of preparation method of compound oil-water separating agent - Google Patents

A kind of preparation method of compound oil-water separating agent Download PDF

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CN107999030A
CN107999030A CN201711132831.4A CN201711132831A CN107999030A CN 107999030 A CN107999030 A CN 107999030A CN 201711132831 A CN201711132831 A CN 201711132831A CN 107999030 A CN107999030 A CN 107999030A
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water
bamboo fibre
separating agent
oil
chitosan
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CN107999030B (en
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刘俊稚
葛亚明
陈庆国
穆军
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Zhejiang Ocean University ZJOU
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Zhejiang Ocean University ZJOU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The present invention relates to oiliness sewage treatment and oil spill recovery technique field, more particularly to a kind of preparation method of compound oil-water separating agent, first by albumen powder, calcium carbonate and phosphoric acid, which are mixed and is mixed in water glass solution, forms mixture, then bamboo fibre nano particle is added, it is dry after modification of chitosan, hardening, cleaning obtains compound oil-water separating agent, bamboo fibre nano particle uses after loading nanometer titanium dioxide silica aerogel, modification of chitosan is mixed to get by Fluorinse of the chitosan with low concentration in acetic acid/sodium acetate buffer solution that pH value is 4~5.Bamboo fibre nano particle, modification of chitosan, calcium phosphate and protein hydrolysed mix load on silica dioxide gel the spatial network structure for forming various dimensions, make oil-water separating agent that there is superpower hydrophilic, water absorbing capacity and storage capacity, absorption speed is fast, the efficient of water body is separated and recovered from greasy dirt water body, and the stability of oil-water separating agent and intensity are good.

Description

A kind of preparation method of compound oil-water separating agent
Technical field
The present invention relates to oiliness sewage treatment and oil spill recovery technique field, and in particular to a kind of compound grease The preparation method of release agent.
Background technology
Increased in recent years with the prosperity and development of modern industry, oily waste water yield and oil spill accident risk, oil-containing If waste water is dealt with improperly or directly discharged, water body nearby can be polluted, aquatic ecosystem is destroyed, can also pass through contaminated soil, sky Gas etc. causes irreversible injury to health and ecological environment, and soil hardening can be caused as oily waste water penetrates into soil, wherein The organic exhaust gas evaporated can threaten health.The material that currently there are the hydrophilic and oleophobic property that species is enriched is used Separated in by grease, but there are low separation efficiency, it is small to the saturated adsorption capacity of water the problem of.
The content of the invention
For existing absorbent material there are the problem of, it is an object of the invention to provide a kind of compound oil-water separating agent Preparation method, by this method prepare oil-water separating agent there is larger oleophobic angle and stronger hydrophilic absorbent ability, by it Coated on boiomacromolecule film, successfully the heavy oils such as crude oil, heavy oil can be isolated with hydrone.
The present invention provides following technical solution：
A kind of preparation method of compound oil-water separating agent, comprises the following steps：
(1) albumen powder, calcium carbonate and mass volume ratio are mixed for 80% phosphoric acid, the mass ratio of three is 0.2:1:5~7, so Ultrasonic wave added in the water glass solution of 2wt%~3wt% is put into afterwards to react to obtain mixture, water glass solution and above-mentioned phosphoric acid Volume ratio be 2~3:1；
(2) by bamboo fibre nano particle that parts by weight are 10~30 parts, 15~23 parts of modification of chitosan is added in step (1) 50~70 parts of mixture in stir and evenly mix, at 20~28 DEG C keep 2~5 it is small when obtain viscous gum；
(3) viscous gum is dried under vacuum to water content and obtains solid powder for 25wt%~35wt%, then at CO2In atmosphere Hardening；
(4) by the solid powder of hardening, vacuum drying obtains compound oil-water separating agent after deionized water is cleaned 2~5 times.
Albumen powder, calcium carbonate and phosphoric acid are mixed and is mixed in water glass solution first in the method for the present invention and forms viscoid System, then dry, hardening, cleaning obtain compound oil-water separating agent after addition bamboo fibre nano particle, modification of chitosan, its Hydrophilic calcium phosphate and amino acid are formed after the middle mixing by albumen powder, calcium carbonate and phosphoric acid, while calcium phosphate plays arrive binding agent Effect, hydrophilic cross-linked network is cooperatively formed with waterglass.Bamboo fibre there is abundant capillary pipe structure due to internal and With superpower water absorbing properties and moment water absorbing capacity, chitosan is one kind by 2- amino-glucose and N-2- acetyl group -2- ammonia The straight-chain polysaccharide without side chain that base-glucose is tied by β-Isosorbide-5-Nitrae glycosidic bond, rich in abundant hydrophilic radical, including Hydroxyl, amino, carbonyl and acetyl group etc., therefore after bamboo fibre nano particle, modification of chitosan are added to above-mentioned cross-linked network Form the compound system with super-strong moisture absorbing ability.CO is carried out after the viscous gum of gained is dried2Hardening, make waterglass by Sodium carbonate and silica dioxide gel skeleton are crossfaded into, sodium carbonate is removed by deionized water cleaning, makes albumen powder and is hydrolyzed into Amino acid, calcium phosphate, bamboo fibre nano particle and modification of chitosan are supported on silica dioxide gel skeleton, form various dimensions Hydrophilic, water suction and water storage network structure, the oil-water separating agent for making gained compound have superpower hydrophilic and water absorbing capacity.
One kind as the method for the present invention is improved, and bamboo fibre nano particle is made through procedure below：By bamboo wood through routine Bamboo chip processed, boiling-off, crushing is decomposed, bamboo fibre is made in boiling bamboo silk, biological enzyme degumming technique, and bamboo fibre is placed in and is persistently connected with CO2Ageing oven in, adjust CO2Flow is 100~150mL/min, and with the speed heat ageing stove of 5~8 DEG C/min 400 ~500 DEG C of 3~6h of holding, then adjust CO2Flow is for 300~360mL/min and with the speed heating aging of 1~2 DEG C/min Stove keeps 2~3h at 800~900 DEG C, stops CO2It is passed through and deionized water 2~3min of steam spray is added into ageing oven, goes The volume ratio of de-ionized water vapor and ageing oven is 0.6~0.7:1, then start the bamboo fibre that cooling is carbonized, then mill To the bamboo fibre nano particle of 10~20nm of particle diameter.It is high by being placed in through bamboo fibre natural made of common process in oxygen barrier environment Temperature charing forms charcoal, makes the intensity of bamboo fibre be strengthened, and removes the organic impurities of inside.Adopted in carbonization process Heated up with the stage and adjust CO2The mode of flow, the heating rate in low temperature calcination stage first is fast, and is continually fed into CO2To promote The formation of bamboo fibre central hole structure, while CO2The acid atmosphere for being dissolved in the moisture formation discharged in charing can be with enhanced biological charcoal The stability of C-O skeletons and the formation of-COO-, be then to slowly warm up to higher calcining heat with enhanced biological charcoal skeleton and The intensity of pore structure, stability of the increase bamboo charcoal in water body.Deionized water steam spray is added after high-temperature calcination, makes bamboo fibre Quick refrigeration disappears fire, complex porous structure is produced in bamboo fibre, surface area increase several times, are significantly increased water absorbing capacity, pass through The water absorption capacity of bamboo fibre nano particle is big made of above process processing, and rate of water absorption is fast, and intensity is high.
One kind as the method for the present invention is improved, and bamboo fibre nano particle uses after procedure below is handled：By bamboo fibre Nano particle is with nanometer titanium dioxide silica aerogel using mass ratio as 1:0.2~0.5 mixing, then adjusting pressure and temperature makes dioxy It is in a supercritical state to change titanium aeroge, nanometer titanium dioxide is made with decompression immediately after 100~120rpm/min vibrations, 30~60min Silica aerogel is supported on bamboo fibre nano particle.Silicone hydroxyl in aerosil can form hydrogen bond with water, have Stronger water absorbing capacity, while aerosil inner pore structure-rich, storage capacity is strong, therefore by silica airsetting Glue, which is loaded on bamboo fibre nano particle, makes the formation of the pore passage structure of aeroge and bamboo fibre nano particle interlock, comprehensive water storage energy Power is better than both respective water storage effects, and the compatibility of the aerosil and silica dioxide gel skeleton is good, can To strengthen the stability of oil-water separating agent.
One kind as the method for the present invention is improved, and the modification of chitosan is made through procedure below：Chitosan is placed in pH It is worth the acetic acid for 4~5/sodium acetate buffer solution to mix, adds Fluorinse and stir evenly, then protected at 23~28 DEG C Hold 2~3 it is small when obtain mixed system；Mixed system is placed in vacuum environment after drying, is cleaned 2~5 times through deionized water To modification of chitosan.It is 4~5 to be placed in the Fluorinse of low concentration and adjust pH chitosan, makes the amino on chitosan Positively ionized forms ammonia radical ion, so that with reference to fluorine ion, the formation-F end groups group in chitosan, has and form hydrogen bond with water Ability, the water absorbing capacity of modification of chitosan lift 15%~20% compared with chitosan.
One kind as the method for the present invention is improved, Fluorinse 0.1~0.2mol/L of concentration, acetic acid/acetate buffer Solution and Fluorinse volume ratio 3~7:1, sodium fluoride is with chitosan mass than 1:6~9.The suitable proportioning of control, ensures whole The pH value of solution is 4~5 in a modifying process, has both made amino of chitosan positively ionized, while fill the sodium ion in sodium fluoride Divide and enter in acetic acid/sodium acetate buffer solution system, discharge fluorine ion.
One kind as the method for the present invention is improved, and the hardening process in step (3) is as follows：Solid powder is being connected with CO2 Air passage in dispel out, adjust CO2Flow for 50~70mL/min and keep 60~90min, then increase CO2Flow extremely 150~200mL/min simultaneously keeps 120~180min.Stage shape changes CO2 wind flows in air passage, is sufficiently hardened waterglass And ensure that silica dioxide gel skeleton is intact.
One kind as the method for the present invention is improved, and vacuum drying temperature is 15~28 DEG C.Low-temperature vacuum drying protection is more Tie up the integrality of network structure.
Beneficial effects of the present invention are as follows：
In compound oil-water separating agent prepared by the method for the present invention, bamboo fibre nano particle, modification of chitosan, calcium phosphate and egg White matter hydrolysed mix loads on silica dioxide gel the spatial network structure for forming various dimensions, has oil-water separating agent superpower Hydrophilic, water absorbing capacity and storage capacity, absorption speed is fast, the efficient of water body is separated and recovered from greasy dirt water body, and The stability and intensity of oil-water separating agent are good.
Embodiment
Just the embodiment of the present invention is described further below.
Unless otherwise instructed, the raw material employed in the present invention is commercially available or commonly used in the art, such as Without special instruction, the method in following embodiments is the conventional method of this area.
Embodiment 1
A kind of preparation method of compound oil-water separating agent, comprises the following steps：
(1) albumen powder, calcium carbonate and mass volume ratio are mixed for 80% phosphoric acid, three's mass ratio is 0.2:1:5, then put into Into the water glass solution of 2wt%, ultrasonic wave added reacts to obtain mixture, and the volume ratio of water glass solution and 80% phosphoric acid is 2:1；
(2) stirred in the mixture 50g that the modification of chitosan of the bamboo fibre nano particle of 10g, 15g is added in step (1) Mix, viscous gum is obtained when holding 2 is small at 20 DEG C；
(3) water content will be dried under vacuum at 15 DEG C of viscous gum and obtains solid powder for 35wt%, then at CO2It is hard in atmosphere Change, hardening process is as follows：Solid powder is being connected with CO2Air passage in dispel out, adjust CO2Flow 50mL/min and to protect 60min is held, then increases CO2Flow to 150mL/min and keep 120min；
(4) by the solid powder of hardening, 15 DEG C of vacuum drying obtain compound oil-water separating agent after deionized water is cleaned 2 times.
Wherein, the bamboo fibre nano particle in step (2) is made through procedure below：By processed bamboo chip of the bamboo wood through routine, boil Refining, crushing are decomposed, bamboo fibre is made in boiling bamboo silk, biological enzyme degumming technique, and bamboo fibre is placed in and is persistently connected with CO2Ageing oven In, adjust CO2Flow is 100mL/min, and keeps 6h at 400 DEG C with the speed heat ageing stove of 5 DEG C/min, then adjusts CO2 Flow is warming up to 800 DEG C of 2~3h of holding for 300mL/min and with the speed of 1 DEG C/min, and stopping is passed through CO2And into ageing oven The volume ratio of addition deionized water steam spray 2min, deionized water steam and ageing oven is 0.6:1, then start cooling and obtain The bamboo fibre of charing, then mill to obtain the bamboo fibre nano particle of particle diameter 10nm.
Modification of chitosan in step (2) is made through procedure below：Chitosan is placed in acetic acid/sodium acetate that pH value is 4 Buffer solution mixes, and the Fluorinse for adding 0.1mol/L stirs evenly, wherein acetic acid/sodium acetate buffer solution and fluorination Sodium solution volume ratio 3:1, sodium fluoride is with chitosan mass than 1:6, obtain mixed system when then holding 2 is small at 23 DEG C；Will Mixed system is placed at 15 DEG C in vacuum environment after drying, is cleaned 2 times through deionized water and is obtained modification of chitosan.
Embodiment 2
A kind of preparation method of compound oil-water separating agent, comprises the following steps：
(1) albumen powder, calcium carbonate and mass volume ratio are mixed for 80% phosphoric acid, three's mass ratio is 0.2:1:6, then put into Into the water glass solution of 2.5wt%, ultrasonic wave added reacts to obtain mixture, and water glass solution and 80% phosphoric acid volume ratio are 2.5: 1；
(2) stirred in the mixture 60g that the modification of chitosan of the bamboo fibre nano particle of 20g, 19g is added in step (1) Mix, viscous gum is obtained when holding 3.5 is small at 24 DEG C；
(3) water content will be dried under vacuum at 23 DEG C of viscous gum and obtains solid powder for 30wt%, then at CO2It is hard in atmosphere Change, hardening process is as follows：Solid powder is being connected with CO2Air passage in dispel out, adjust CO2Flow 60mL/min and to protect 75min is held, then increases CO2Flow to 170mL/min and keep 150min；
(4) by the solid powder of hardening, 24 DEG C of vacuum drying obtain compound oil-water separating agent after deionized water is cleaned 4 times.
Wherein, the bamboo fibre nano particle in step (2) is made through procedure below：By processed bamboo chip of the bamboo wood through routine, boil Refining, crushing are decomposed, bamboo fibre is made in boiling bamboo silk, biological enzyme degumming technique, and bamboo fibre is placed in and is persistently connected with CO2Ageing oven In, adjust CO2Flow is 120mL/min, and keeps 4h at 450 DEG C with the speed heat ageing stove of 7 DEG C/min, then adjusts CO2 Flow is warming up to 850 DEG C of holding 2.5h for 330mL/min and with the speed of 1.5 DEG C/min, stops CO2It is passed through and into ageing oven The volume ratio of addition deionized water steam spray 2.5min, deionized water steam and ageing oven is 0.65:1, then start to cool down The bamboo fibre carbonized, then mill to obtain the bamboo fibre nano particle of particle diameter 15nm.
Modification of chitosan in step (2) is made through procedure below：Chitosan is placed in acetic acid/acetic acid that pH value is 4.5 Sodium buffer solution mixes, and the Fluorinse for adding 0.15mol/L stirs evenly, wherein acetic acid/sodium acetate buffer solution with Fluorinse volume ratio 5:1, sodium fluoride is with chitosan mass than 1:7.5, mixed when then holding 2.5 is small at 25 DEG C System；Mixed system is placed at 23 DEG C drying in vacuum environment, is cleaned 4 times through deionized water and obtains modification of chitosan.
Embodiment 3
A kind of preparation method of compound oil-water separating agent, comprises the following steps：
(1) albumen powder, calcium carbonate and mass volume ratio are mixed for 80% phosphoric acid, the mass ratio of three is 0.2:1:7, then throw Enter into the water glass solution of 3wt% ultrasonic wave added and react to obtain mixture, the volume ratio of water glass solution and 80% phosphoric acid is 3: 1；
(2) stirred in the mixture 70g that the modification of chitosan of the bamboo fibre nano particle of 30g, 23g is added in step (1) Mix, viscous gum is obtained when holding 5 is small at 28 DEG C；
(3) water content will be dried under vacuum at 28 DEG C of viscous gum and obtains solid powder for 25wt%, then at CO2It is hard in atmosphere Change, hardening process is as follows：Solid powder is being connected with CO2Air passage in dispel out, adjust CO2Flow 70mL/min and to protect 90min is held, then increases CO2Flow to 200mL/min and keep 180min；
(4) by the solid powder of hardening, 28 DEG C of vacuum drying obtain compound oil-water separating agent after deionized water is cleaned 5 times.
Wherein, the bamboo fibre nano particle in step (2) is made through procedure below：By processed bamboo chip of the bamboo wood through routine, boil Refining, crushing are decomposed, bamboo fibre is made in boiling bamboo silk, biological enzyme degumming technique, and bamboo fibre is placed in and is persistently connected with CO2Ageing oven In, adjust CO2Flow is 150mL/min, and keeps 6h at 500 DEG C with the speed heat ageing stove of 8 DEG C/min, then adjusts CO2 Flow is warming up to 900 DEG C of holding 3h for 360mL/min and with the speed of 2 DEG C/min, stops CO2It is passed through and is added into ageing oven The volume ratio of deionized water steam spray 3min, deionized water steam and ageing oven is 0.7:1, then start cooling and carbonized Bamboo fibre, then mill to obtain the bamboo fibre nano particle of particle diameter 20nm.
Modification of chitosan in step (2) is made through procedure below：Chitosan is placed in acetic acid/sodium acetate that pH value is 5 Buffer solution mixes, and the Fluorinse for adding 0.2mol/L stirs evenly, wherein acetic acid/sodium acetate buffer solution and fluorination Sodium solution volume ratio 7:1, sodium fluoride is with chitosan mass than 1:9, obtain mixed system when then holding 3 is small at 28 DEG C；Will Mixed system is placed in vacuum environment after drying, is cleaned 5 times through deionized water and is obtained modification of chitosan.
Embodiment 4
A kind of preparation method of compound oil-water separating agent, difference from Example 1 be, the bamboo fibre in step (2) Nano particle uses after procedure below is handled again after above-mentioned technique is made：By bamboo fibre nano particle and nano silicon dioxide Aeroge is using mass ratio as 1:0.2 mixing, then adjusting pressure and temperature makes titania aerogel in a supercritical state, with Decompression immediately makes nano silicon dioxide aerogel carried on bamboo fibre nano particle after 100rpm/min vibrations 60min.
Embodiment 5
A kind of preparation method of compound oil-water separating agent, difference from Example 1 are that bamboo fibre is received in step (2) Rice grain uses after procedure below is handled again after above-mentioned technique is made：By bamboo fibre nano particle and nano silicon dioxide gas Gel is using mass ratio as 1:0.4 mixing, adjusting pressure and temperature makes titania aerogel in a supercritical state, with Decompression immediately makes nano silicon dioxide aerogel carried on bamboo fibre nano particle after 110rpm/min vibrations 45min.
Embodiment 6
A kind of preparation method of compound oil-water separating agent, difference from Example 1 are that bamboo fibre is received in step (2) Rice grain uses after procedure below is handled again after above-mentioned technique is made：By bamboo fibre nano particle and nano silicon dioxide gas Gel is using mass ratio as 1:0.5 mixing, then adjusting pressure and temperature makes titania aerogel in a supercritical state, with Decompression immediately makes nano silicon dioxide aerogel carried on bamboo fibre nano particle after 120rpm/min vibrations 60min.
Hydrophilic and oleophobic performance test
1. water absorbing capacity is tested：The oil-water separating agent of the gained of embodiment~embodiment 6 of 2g is respectively taken, is then respectively placed in and fills In the beaker of 100g water, 23 ± 2 DEG C it is quiet put 48 it is small when, then take out weighing weight, the difference for calculating two inferior qualities is to inhale Water, and water absorption rate is calculated, water absorption is water absorption and the percentage of 2g, and the results are shown in Table 1.
2. oleophobic performance test：The oil that each oil-water separating agent in embodiment 1~6 is measured using contact angle tester is contacted Angle, test result are shown in Table 1
1 test result of table
Experimental group Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Water absorption/g 0.782 0.822 0.810 0.904 0.915 0.908
Water absorption rate/% 39.1 41.1 40.5 45.2 45.8 45.4
Oleophobic angle 82° 87° 84° 93° 95° 93°

Claims (7)

1. a kind of preparation method of compound oil-water separating agent, comprises the following steps：
（1）The phosphoric acid that albumen powder, calcium carbonate and mass volume ratio are 80% is mixed, three's mass ratio is 0.2:1:5~7, then Ultrasonic wave added in the water glass solution of 2wt%~3wt% is put into react to obtain mixture, the body of water glass solution and above-mentioned phosphoric acid Product is than being 2~3:1；
（2）By parts by weight be 10~30 parts bamboo fibre nano particle, 15~23 parts of modification of chitosan be added to step（1）In 50~70 parts of mixture in stir and evenly mix, at 20~28 DEG C keep 2~5 it is small when obtain viscous gum；
（3）Viscous gum is dried under vacuum to water content and obtains solid powder for 25wt%~35wt%, then at CO2It is hard in atmosphere Change；
（4）By the solid powder of hardening, vacuum drying obtains compound oil-water separating agent after deionized water is cleaned 2~5 times.
2. the preparation method of oil-water separating agent according to claim 1, it is characterised in that bamboo fibre nano particle is through following Process is made：Bamboo fibre is made through conventional bamboo chip processed, boiling-off, crushing decomposition, boiling bamboo silk, biological enzyme degumming technique in bamboo wood Dimension, bamboo fibre is placed in and is persistently connected with CO2Ageing oven in, adjust CO2Flow is 100~150 mL/min, and with 5~8 DEG C/ The speed heating ageing oven of min keeps 3~6h at 400~500 DEG C, then adjusts CO2Flow is for 300~360mL/min and with 1 The speed heating ageing oven of~2 DEG C/min keeps 2~3h at 800~900 DEG C, stops CO2It is passed through and is added into ageing oven and is gone The volume ratio of de-ionized water vapor 2~3min of spraying, deionized water steam and ageing oven is 0.6~0.7:1, then start to cool down To the bamboo fibre of charing, then mill to obtain the bamboo fibre nano particle of 10~20nm of particle diameter.
3. the preparation method of oil-water separating agent according to claim 1 or 2, it is characterised in that bamboo fibre nano particle passes through Used after procedure below processing：By bamboo fibre nano particle and nanometer titanium dioxide silica aerogel using mass ratio as 1:0.2~0.5 is mixed Close, then adjust pressure and temperature make titania aerogel in a supercritical state, with 100~120rpm/min vibration 30~ Decompression makes nano silicon dioxide aerogel carried on bamboo fibre nano particle immediately after 60min.
4. the preparation method of oil-water separating agent according to claim 1, it is characterised in that the modification of chitosan is through following Process is made：Chitosan is placed in acetic acid/sodium acetate buffer solution that pH value is 4~5 to mix, adds Fluorinse stirring Uniformly, mixed system is obtained when then holding 2~3 is small at 23~28 DEG C, mixed system is placed in vacuum environment after drying, Cleaned 2~5 times through deionized water and obtain modification of chitosan.
5. the preparation method of oil-water separating agent according to claim 4, it is characterised in that Fluorinse concentration 0.1~ 0.2mol/L, acetic acid/sodium acetate buffer solution and Fluorinse volume ratio 3~7:1, sodium fluoride is with chitosan mass than 1:6 ~9.
6. the preparation method of oil-water separating agent according to claim 1, it is characterised in that step（3）In hardening process It is as follows：Solid powder is being connected with CO2Air passage in dispel out, adjust CO2Flow for 50~70mL/min and keep 60~ 90min, then increases CO2Flow to 150~200mL/min and keep 120~180min.
7. the preparation method of oil-water separating agent according to claim 1, it is characterised in that step（3）And step（4）In it is true The dry temperature of sky is 15~28 DEG C.
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CN113521881A (en) * 2021-07-23 2021-10-22 江西离子型稀土工程技术研究有限公司 Filter cloth for treating oil-containing wastewater generated in rare earth smelting and preparation method thereof
CN113694877A (en) * 2021-08-24 2021-11-26 天津朗华科技发展有限公司 Selective adsorbent for gasoline purification and preparation method and application thereof
CN114214111A (en) * 2021-12-29 2022-03-22 安美科技股份有限公司 Process for purifying, regenerating and recycling old hydraulic oil

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